Preparation of transition metal oxide thin films used as solar absorbers

233 Pages·2017·10.97 MB·English

by  Thi Ly Le

Preparation of transition metal oxide thin films used as
solar absorbers
Thi Ly Le
To cite this version:
Thi Ly Le. Preparation of transition metal oxide thin films used as solar absorbers. Materials.
Université Paul Sabatier - Toulouse III, 2016. English. ￿NNT: 2016TOU30120￿. ￿tel-01578163￿
HAL Id: tel-01578163
https://theses.hal.science/tel-01578163
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En vue de l’obtention du

DOCTORAT DE L’UNIVERSITÉ DE TOULOUSE

Université Toulouse 3 Paul Sabatier (UT3 Paul Sabatier)

Présentée et soutenue par :
Thi Ly LE
le vendredi 30 septembre 2016
Titre:
PREPARATION OF TRANSITION METAL OXIDE THIN FILMS
USED AS SOLAR ABSORBERS

École doctorale et discipline ou spécialité :
ED SDM : Sciences et génie des matériaux – CO034

Unité de recherche:
UMR 5085 CIRIMAT – Centre Inter-Universitaire de Recherche et d’Ingénierie des Matériaux

Directeur/trice(s) de Thèse :
Sophie GUILLEMET-FRITSCH
Christophe TENAILLEAU
Jury:

André AYRAL Professeur, IEM, Montpellier Rapporteur
Fabrice ROSSIGNOL Directeur de Recherche, SPCTS, Limoges Rapporteur
Catherine AMIENS Professeur, LCC, Toulouse Examinateur
Dinh Phong TRAN Docteur, USTH Hanoï, Vietnam Examinateur
Sophie GUILLEMET-FRITSCH Directeur de Recherche, CIRIMAT, Toulouse Examinateur
Christophe TENAILLEAU Maître de Conférences, CIRIMAT, Toulouse Examinateur
Pascal DUFOUR Maître de Conférences, CIRIMAT, Toulouse Invité

ACKNOWLEDGEMENTS

In 2nd October 2013, I started as a PhD student in the Centre Inter-Universitaire de Recherche
et d’Ingénierie des Matériaux (CIRIMAT) laboratory. My three-years journey arrived to its end,
with all its fine and became to a part of my life. The journey would not have succeeded without
the cooperation and encouragement I received all along.
First of all, I would like to thank Dr. Philippe TAILHADES, the director of CIRIMAT for
accepting me in the laboratory. I appreciate the working conditions and the warming reception.
Thanks to the Vietnamese government and University of Sciences and Technology in Hanoi
(USTH) program, that opened the door of research for me in Toulouse.
I am very thankful to two reviewers of my manuscript, Professor André AYRAL and Research
Director Fabrice ROSSIGNOL, as well as all the jury members, Dr. Dinh Phong TRAN and
Professor Catherine AMIENS. Thank you for your time and your expertise.
My deepest and most sincere gratitude goes to my supervisors, Sophie GUILLEMET-
FRITSCH, Christophe TENAILLEAU and Pascal DUFOUR, who have guided me through the
doctoral research. I would like to thank you for giving me support and encouragement. Special
thanks to you for your kindness and enthusiasm, for providing me valuable suggestions in
research. Without your help, my thesis would not have been possible.
I would like to thank Professor Juan Claudio Nino from University of Florida, who has guided
me to prepare the thin films by Pulsed Laser Deposition method and Dr. Rémis Arras from
CEMES (Centre d’élaboration de Matériaux et d’études structurales) who calculated and
explained for me about the first-principles electronic structure calculation.
I would like to thank equally to people who provided me logistic, administrative and technical
assistance, Marie-Claire, Murielle, Nabila, Maryse, Isabelle, Benjamin, Abdé, Vincent, Yohan,
Jean-Jaque… from CIRIMAT. Thank you for your kindness and easy going manner of work.
Thanks to all the colleagues in CIRIMAT. Thank you Mai Anh and Hoa for sharing all the tips
and helping me all the papers that I needed for my first days in laboratory. Sébastien, Tawfik,
Hyksu, Mong Cam, Soufiane, Nahum, Precious, Elsa, thank you for the friendly atmosphere in
the office and all the encouragement during the last few months of my thesis. I had with you in
the office and in the lab will be part of good memories in my life. Thank you Candida, Luciana,
Cyril, Inthuga, Pauline…Thank you all for sharing good moments with me.
I want to thank all my friends from Vietnam, Hoa & Nhi, Viet & Thu, Thao, Yen, Tam, Dung,
Thuy, Trung…Thank you all for sharing with me the great moments apart from work no matter
where, thank you for your support from everywhere, and most importantly thank you for your
confidence in me. Thank you Yen and Tam for helping me to prepare the party for my defense.
From bottom of my heart, I would like to express my honest gratitude to my family for love and
encouragement. Thank for them, I always be on the right track.
All my thanks,
LE Thi Ly.
TABLE OF CONTENTS
LIST OF ABBREVIATIONS .................................................................................................... i
GENERAL INTRODUCTION .................................................................................................... 1
General introduction ................................................................................................................ 1
CHAPTER I ................................................................................................................................ 5
TOWARDS ALL-OXIDE SOLAR CELLS ........................................................................... 5
I.1. Introduction........................................................................................................................ 7
I.1.1. Decreases in fossil fuels reserves ........................................................................... 7
I.1.2. Climate change and global warming..................................................................... 9
I.2. Renewable energy: Energy of the future ....................................................................... 10
I.2.1. Wind power ........................................................................................................... 10
I.2.2. Hydroelectric energy ............................................................................................ 11
I.2.3. Biomass energy ...................................................................................................... 12
I.2.4. Geothermal energy ............................................................................................... 13
I.2.5. Solar energy ........................................................................................................... 13
I.3. Most familiar generations of photovoltaic cells ............................................................ 14
I.3.1. First generation of photovoltaic cells .................................................................. 15
I.3.2. Second generation of photovoltaic cells .............................................................. 16
I.3.3. Third generation of photovoltaic cells ................................................................ 18
I.4. Metal Oxide semiconductors for photovoltaic cells ...................................................... 20
I.4.1. n-type wide band gap metal oxides ..................................................................... 20
I.4.2. p-type metal oxide light absorbers ...................................................................... 22
I.5. All-oxide photovoltaics: The next generation of photovoltaic cells? .......................... 24
I.5.1. Cu2O based “all-oxide” photovoltaics ................................................................. 25
I.5.2. Perovskite solar cells (PSCs) ................................................................................ 27
I.5.3. Spinel oxide solar cells .......................................................................................... 29
I.6. Mixed valence spinel oxides as solar absorbers ............................................................ 31
I.6.1. Crystal structure ................................................................................................... 31
I.6.2. Electrical conductivity .......................................................................................... 34
I.6.3. Optoelectronic properties .................................................................................... 35
I.6.4. Transition metal (Ni or Cu or Zn)-doped cobalt-based spinel systems ........... 38
I.7. References ......................................................................................................................... 41
CHAPTER II ............................................................................................................................. 51
EXPERIMENTAL TECHNIQUES.................................................................................... 51
II.1. Introduction .................................................................................................................... 53
II.2. Preparation methods ...................................................................................................... 53
II.2.1. Powder synthesis ................................................................................................. 53
II.2.2. Thin film deposition ............................................................................................ 54
II.2.3. Elaboration of dense ceramics ........................................................................... 57
II.2.4. Conventional sintering ........................................................................................ 60
II.3. Analyses techniques ....................................................................................................... 60
II.3.1. Analysis of chemical compositions by X-ray fluorescence (XRF) .................. 60
II.3.2. Analysis of crystalline structure by X-ray diffraction (XRD) ......................... 61
II.3.3. Microstructural analysis by Field Emission Gun Scanning Electron
Microscope (FEG-SEM) ................................................................................................ 64
II.3.4. Thermal gravimetric analysis (TGA) ................................................................ 66
II.3.5. Thermal mechanical analysis (TMA) or dilatometry ...................................... 67
II.3.6. Topographic and roughness surfaces of thin films .......................................... 68
II.3.7. Optical measurements ........................................................................................ 69
II.3.8. Electrical properties of the thin films ................................................................ 72
II.4. References ....................................................................................................................... 73
CHAPTER III ........................................................................................................................... 75
FIRST-PRINCIPLES ELECTRONIC STRUCTURE CALCULATIONS FOR THE
WHOLE SPINEL OXIDE SOLID SOLUTION RANGE MnxCo3-xO4 (0 ≤ x ≤ 3) ............. 75
III.1. Introduction .................................................................................................................. 77
III.2. Atomic, magnetic and electronic structures of Mn and Co spinel oxides ............... 78
III.2.1. Co3O4 ................................................................................................................... 78
III.2.2. Mn3O4 ................................................................................................................. 81
III.2.3. MnxCo3-xO4 ......................................................................................................... 86
III.3. Conclusion ..................................................................................................................... 98
III.4. References .................................................................................................................... 100
CHAPTER IV .......................................................................................................................... 107
SYNTHESIS AND CHARACTERIZATION OF POWDERS AND THIN FILMS OF
SPINEL OXIDES MxCo2-xMnO4 (M = Ni, Cu, Zn; x = 0, 0.15, 0.30, 0.60) .................. 107
IV.1. Introduction ................................................................................................................. 109
IV.2. Synthesis and characterization of the powders ........................................................ 110
IV.2.1. Synthesis ........................................................................................................... 110
IV.2.2. Characterization of the powders .................................................................... 112
IV.3. Preparation and characterization of thin films ........................................................ 130
IV.3.1. Stabilization of colloidal dispersion ................................................................ 131
IV.3.2. Thin films preparation using the dip-coating technique .............................. 132
IV.3.3. Characterization of thin films ......................................................................... 133
IV.4. Characterization of thin films after heat treatment ................................................ 137
IV.4.1. Structural determination by Grazing Incidence X-ray Diffraction
(GI-XRD) ....................................................................................................................... 137
IV.4.2. Microstructure characterization determined by Field Emission Gun
Scanning Electron Microscope (FEG-SEM) .............................................................. 142
IV.5. Conclusion ................................................................................................................... 146
IV.6. References .................................................................................................................... 148
CHAPTER V ........................................................................................................................... 151
PHYSICAL PROPERTIES OF SPINEL OXIDE THIN FILMS M Co MnO (M = Ni, Cu,
x 2-x 4
Zn; x = 0, 0.15, 0.30, 0.60) AND CHARACTERIZATION OF THIN FILMS PREPARED
BY PULSED LASER DEPOSITION ............................................................................... 151
V.1. Introduction .................................................................................................................. 153
V.2. Physical properties of spinel oxide thin films deposited by the dip-coating technique
................................................................................................................................................ 153
V.2.1. Optical properties .............................................................................................. 153
V.2.2. Electrical properties of the spinel oxide thin films ......................................... 172
V.3. Preparation and study of spinel oxide and cuprite thin films deposited by the PLD
technique ............................................................................................................................... 178
V.3.1. Thin films preparation ...................................................................................... 178
V.3.2. Characterization of the oxide thin films deposited by the PLD method ...... 179
V.4. Conclusion ..................................................................................................................... 183
V.5. References ..................................................................................................................... 185
GENERAL CONCLUSION AND FUTURE WORK ............................................................... 189
LIST OF ABBREVIATIONS

AALD Atmospheric Atomic Layer Deposition
ASR Area Specific Resistance
AZO Aluminium doped Zinc Oxide
CB Conduction Band
CCD Charge Coupled Device
CET Coefficient of Temperature Expansion
CIGS Copper Indium Gallium Selenide
CIS Copper Indium Selenide
CMOS Complementary Metal Oxide Semiconductor
CNG Compressed Natural Gas
CSD Chemical Solution Deposition
CZTS Copper Zinc Tin Sulfide
DFT Density Function Theory
DOS Density Of States
DSSC Dye Sensitized Solar Cells
EQE External Quantum Efficiency
FEG-SEM Field Emission Gun Scanning Electron Microscope
FTO Fluorine doped Tin Oxide
FWHM Full Width at Half Maximum
GI-XRD Grazing Incidence X-Ray Diffraction
HTM Hold Transport Material
ICP-AES Induced Coupled Plasma Atomic Emission Spectrometry
IQE Internal Quantum Efficiencies
ITO Indium Tin Oxide
MOS Metal Oxide Semiconductor
P25 Degussa, average size equal to 25 nm of TiO
2
PES Photoemission Spectroscopy
PLD Pulsed Laser Deposition
PLZT (Pb, La)(Zr, Ti)O
3
PMMA Polymethylmethacrylate
PSCs Perovskite Solar Cells
PV Photovoltaic